Fact Sheets on Production, Use and Release of Priority Substances in the Wfdroyal Haskoning

Fact sheets on production, use and release of priority substances in the WFDRoyal Haskoning

1,2-Dichloromethane, final draft

For official use only

Draft version: final draft (previous version: 3.3)

Status date: 30 september 2002

Comments:

• changed format
• remarks of EU letter ENV B.1/PMM/JD’E/ipD (2002) 310893 (30-7-02) incorporated
• section measures completed

SUBSTANCE: 1,2-Dichloroethane (EDC)
I Chemical identity
CAS number:107-06-2
Chemical group:Chlorinated alkanes
Chemical formula: C2H4Cl2
Homologues:No homologues
Synonyms:Ethylenechloride, ethylenedichloride, ethaan dichloride, acetylene dichloride, ethane, 1,2-dichloro, 2-Dichlorethan; Chlorethylen; Dichlorethan, 1,2-; Dikloretan, 1,2-; EDC; Ethan, 1,2-Dichlor- ; Ethane, 1,2-dichloro- ; Ethylendichlorid ; Ethylenum chloratum ; Freon 150; Holländisches Öl ; NCI C00511 ;
Technical mixtures:Not relevant
II Physical properties
Water solubility:8690 mg/l (20C)
Vapour pressure:8.5 kPa l (20C)
Log Kow:111.5 Pa.m3/mol (25C)
III Production and use in 15 EU member states and accession states

1. Way of production/Process description:

1,2-dichloroethane (EDC) is manufactured by the catalytic vapour-phase or liquid-phase chlorination of ethylene or by oxychlorination of ethylene (with presence of oxygen and HCl). [Archer 1979 in IPCS 1995; Eurochlor, 2000]

1. Fields of application:

EDC is used as an intermediate in the synthesis of vinyl chloride monomer (PVC production) and in the manufacture of various chlorinated solvents. Historical uses were fumigant and anti-knock gasoline additives. [IPCS, 1995; Eurochlor, 2000]

1. Production volume:

More than 1,000,000 tonnes was produced in the UK in 1991 [UK HSE 1992 in IPCS, 1995].
Production in EU in 1998 was about 8.8 million tonnes. [Eurochlor, 2001]
Germany: 2 800 000 t in Jahr 1999[Statistisches Bundesamt, 1999]

1. Number of production sites and locations of production:

Locations of production, reported by IUCLID (2000) are presented in appendix 1.

1. Use volume:

No data in project database available. Assuming that nearly all EDC is converted into VCM (Vinyl Chloride Monomer), this equates to an annual West European EDC production of 9400 Kt [CEFIC, 1999].In Sweden 154,000 tonnes was used in 1999 as raw material for synthesis, in laboratories and in glues. [Swedish EPA, 2001]

1. Relative use volumes in various applications:

• Feedstock for production of Vinyl Chloride Monomer: >98%. For technical reasons (flexibility needed because EDC plants are difficult to run) the EDC capacity is always about 5 to 6 % higher than the capacity requested for VCM production. [Eurochlor, 1997]
• Raw material for ethyleneamines/trichloroethylene/perchloroethylene and some fluorinated substances, extraction and cleaning solvent INDUSTRIAL USE ONLY: <2% [ECVM, 2001]

1. Existing regulation in member states or associated member states:

In the EU, EDC emissions to water are governed by the EC Directive 90/415 of July 27, 1990. Directive 90/415/EC amending Annex II to Directive 86/280 EEC, one of the five "Daughter Directives" of 76/464 [Eurochlor, 1997]
The Emission Limit Value is defined in directive 76/464/EEC. EC (1982) List I within the framework of Directive 76/464/EEC on pollution caused by certain dangerous substances discharged into the aquatic environment of the Community Official Journal C 176, 14/7/1982 p. 7 - 10.
Limit values for drinking water have been established under Directive 98/83/EC and it is also controlled as a VOC under Directive 1999/13/EC. [RPA, 2000]
OSPAR (1998) OSPAR 1998 List of Candidate Substances OSPAR Strategy with regard to Hazardous Substances (Ref. nr. 1998-16), Annex 3. Sintra 22-23 July 1998.

1. Industrial associations to be addressed:

Euro Chlor, ECVM
IV Releases to environment

1. General way of entrance and schematic picture:

Relevant main routes of release to the environment are given in appendix 2 and summarised as follows:
Atmospheric deposition: Industrial use: A5/A6
Waste: A7
Industrial use: S8.4, S9
EDC is released to environment, principally through emissions during production and that of VCM (vinyl chloride monomer). The majority of EDC released to the environment is in emissions to air. Some EDC may be released in industrial effluents to the aquatic environment.

1. Atmospheric cycle:

1. Industrial Point Sources to the air:

Release route: A5 and A6:
Chemical products manufacturing or processing (NOSE 107.03)
By the production of EDC and VCM the emission of EDC to air is 64.1 g/tonne VCM (IPPC, 2002).

1. Municipal Collective Sources to the Air:

Release route: A7
.Incineration of industrial wastes (except flaring) (NOSE 109.03.02)
DCE is recovered from waste streams of manufacturing facilities by distillation operation. This Waste stream is incinerated (destruction efficiency 99.99%) [US EPA 1986 in IPCS, 1995]

1. Diffuse sources to air and deposition:

No relevant data in project database available concerning diffuse sources to air
No relevant data available concerning deposition

1. Aquatic releases:

1. Industrial Point Sources to the aquatic environment

.Production formulation and Industrial Use (release route: S8.4, S9) (NOSE 107)
According to a recent industrial survey (80 sites), the release to water in the EU from production and intermediate use, in 1998 amounted 15 t/a (which is a reduction by factor 10 in 15 years). [Eurochlor, 2001]

1. Municipal Collective Sources to the aquatic environment:

Release route S8.4 and S9.2
Waste water treatment in industry (NOSE 109.02.41)
The emission factor before treatment in a Dutch EDC/VCM plant is 1.8 g/tonne VCM. The effluent load after treatment is 0.03 g/tonne VCM

1. Diffuse sources to water

No relevant data in project database available concerning diffuse sources of water.

1. Overall Releases and Summary:

The mean release of EDC is the emission to air in the EDC/VCM industry. Because EDC is an intermediate, no emission is released during consuming.
V Environmental fate of releases to environment

1. Adsorption to solids (sediment, sludge, soil):

EDC is not expected to adsorb appreciable to soil, suspended solids or sediments. [IPCS, 1995]

1. Volatilisation:

Volatilisation is the major removal process of EDC from the aquatic environment. [IPCS, 1995]

1. Degradation:

Degradation in water is possible, however most is lost due to volatilisation of the compound [IPCS, 1995]
DT50 water (hydrolysis): 23 – 300 years at 15 °C [IUCLID, 2000]
DT50 air 12-121 (ind. Photolyse) [IUCLID, 2000]

1. Partition to compartments:

Due to high vapour pressure, the atmosphere is expected to be the predominant environmental sink for EDC. The estimated atmospheric lifetime is between 43 and 11 days. Long range transport is possible. [IPCS, 1995]
The predicted half-life in eutrophic lake is 9 days and in a 300 km stretch of a river system one day.
EDC may leach to groundwater, based on its solubility, low Kow and high mobility in soil. [IPCS, 1995]
The partition of EDC into the environmental compartments, according to MacKay level I, are: [Mackay et al 1990 in Eurochlor, 1997]
Air: 97.1-97.3%
Water: 2.7-2.9%
Soil: 0.01%
Sediment: 0.01%

1. Behaviour:

The atmosphere is the predominant environmental sink for EDC. Because of the atmospheric lifetime, between 43 and 11 days, EDC will break down easily. The reported degradation products are formyl chloride, hydrogen chloride, carbon dioxide, carbon monoxide, and monochloroacetyl chloride.
VI Evaluation

1. Relevant NOSE-codes of point sources:

NOSE-codeSourcesIPPC-code
107.02Degreasing, dry cleaning and electronics6.7
107.03.02Polyvinylchloride4.1
107.03.06/Pharmaceutical products manufacturing4.5
107.04.10idem4.5
107.03.11Adhesive, magnetic tapes, films and photographs4.1
107.06Use of pesticides (other than agriculture and forestry)
109.02.41Waste water treatment in industry
109.02.42Waste water treatment in residential/commercial sectors
109.03.02Incineration of industrial wastes (except flaring)
n.a.*Aerospace industry
* n.a. = not applicable
According to de Ministry of Spain the following industrial sectors potentially discharges EDC to the environment: oil refining, pesticides, pharmaceutical manufacturing, photographic material manufacturing and aerospace industry. [Ministerio de medio ambiente, 2001]

1. Evaluation of emission data:

1. Emission to water

According to Euro Chlor, 2000, the emission level to water was 15 tons/year in 1998, reducing every year.

1. Emission to air

With a production of 9400 Kt VCM a year and an emission of 64.1 g/ton VCM, the total emission is 602 tons a year. [IPPC, 2002]

1. Deposition

No relevant data in project database available concerning deposition.

1. Gaps and questions:

The mean route is the emission to air, but no exact level is available of this emission.
VII Measures

1. Measures at production level:

1. Contribution to water at production level

No relevant data in project database available concerning the contribution to water at production level.

1. Relevant IPPC sector, documents and available emission criteria

The relevant IPPC sectors are:
-4.1 Chemical installations for the production of basic organic chemicals;
-4.5 Installations using a chemical or biological process for the production of basic pharmaceutical products;
-6.7 Installations for the surface treatment of substances, objects or products using organic solvents.
EDC is mentioned in the IPPC BREF document for large volume organic chemical industry. [IPPC, 2002]
The manufacture and use of EDC is covered by EC Directive 90/415/EEC and is relevant to water releases from the production of vinyl chloride monomer (VCM). This stipulates EDC emission values of <2.5 mg/l or 5g/t of production.
The Oslo and Paris Commission have issued Decision 98/4 on achievable emission levels from EDC/VCM manufacture: for air 5 mg/Nm3 en for water 5 g/t EDC purification capacity or 2.5 mg/l. The decision contains ELVs which have been derived from a BAT technical document and a BAT Recommendation.

1. Voluntary agreements

The European Council of Vinyl Manufactures (ECVM) represents most (11 out of 12) of the European EDC/VCM/PVC producers. In 1994, ECVM issued an industry charter to improve environmental performance and introduce emission levels that were considered achievable on EDC/VCM units. The ECVM charter identifies techniques that represent good practice in the processing, handling, storage and transport of primary feedstock and final products in VCM manufacture. The charter also contains environmental standard for air and water emissions from EDC and VCM production. For EDC an emission value of 5 mg/Nm3 is assigned, and for water 5 g/t EDC purification or a concentration limit of 1 mg/l EDC in the process effluent. [IPPC, 2002]

1. Substitution

Not relevant.

1. Process control, modifications

The BAT route for the production of EDC is via the chlorination of ethylene. The chlorination of ethylene can be carried out by ‘direct chlorination’ or ‘oxychlorination’, each route having its advantages and providing complementary components of the balanced EDC/VCM process, and so it is not possible to identify which one is BAT.
BAT is to optimise the process balancing so as to maximise the recycle of process streams. Where local circumstances do not permit full process balancing, attention is to be paid to optimising the sources and sinks of EDC
When considering the direct chlorination of ethylene, both the low-temperature and high-temperature variants are BAT for new units. For existing ‘cold’ chlorination units the retrofitting of high temperature units is probably not justified.
In the ethylene oxychlorination step, the are choices between the source of oxidant (air or oxygen) and the reactor type (fixed or fluidised bed)
.Source of oxidant: The use of oxygen is considered to be BAT for new plants, provided that there is an economically available source of oxygen. For an air-based unit, the retrofitting of oxygen may be justified by site specific, economic reason
.Reactor type: Fixed bed and fluid bed reactors may both be BAT.
BAT for the recovery of EDC is:
.Recycling directly to the process
.Refrigeration and condensation
.Absorption in solvents followed by stripping; or
.Adsorption on solids followed by desorption.
BAT is to use efficient combustion techniques to further reduce the off-gas concentrations of EDC and to recover energy as steam.

1. Effluent treatment

BAT is treatment of effluent streams arising from:
.Wash water and condensate from EDC purification
.Water seal flushes from pumps, vacuum pumps
.Cleaning water from maintenance operations
.Water separated in wet EDC and light-end storage tanks
BAT for EDC dissolved in water is steam, or hot air, stripping to effluent concentrations of less than 1 mg/l. BAT for the stripped material is condensation and recovery, or incineration.
BAT for EDC absorbed on particulate matter is removal by flocculation, settling and filtration.
On sites where the effluent is still above the criteria, then BAT may, in addition be:
.Micro-filtration by membrane filter for particulates down to 0.5 m
.Adsorption of EDC on activated carbon fixed bed filters.

1. Measures at use level:

1. Contribution to water at use level

No relevant data in project database available concerning the contribution to water at use level.

1. Use by IPPC sectors

See BAT in paragraph VII.1.

1. Use by SME groups

Not relevant

1. Use by consumers

Not relevant

1. Use in agriculture

Not relevant

1. Measures at community level:

1. Sewage treatment

If relevant, see VII.1.f

1. Waste disposal

Not relevant

1. Incineration

Not relevant

1. Recycling

Not relevant

1. Measures at regulatory level:

1. EU level: IPPC emission control

BREF document for large volume organic chemical industry [IPPC, 2002]. Coming BREF documents could be extended with a paragraph about the possibilities of treatment of EDC.

1. EU level: Substitution or outphasing

Not relevant

1. EU level: Limitations of use in certain applications

Not relevant

1. Other regulatory and/or national policy measures

OSPAR (1998) OSPAR 1998 List of Candidate Substances OSPAR Strategy with regard to Hazardous Substances (Ref. nr. 1998-16), Annex 3. Sintra 22-23 July 1998.

Literature

• Anonymous, 2001. Austrian legislation on Priority Chemicals of the Water Framework Directive.
• CEFIC, 1999. EDC/VCM Process BREF : Chapter 1 General Information.
• ECVM, 2001. On the environmental impact of the manufacture of Polyvinylchloride. A description of the best available techniques.

• Eurochlor, 1997. 1,2-Dichloroethane, Euro Chlor risk assessment for the marine environment OSPARCOM region: North Sea.

• Eurochlor, 2000. Euro Chlor risk assessment for the marine environment OSPARCOM region: North sea.

• Eurochlor, 2001. Information sheet on 1,2 Dichloroethane.

• IPCS (International Programme on Chemical Safety), 1995. 1,2-Dichloroethane.Environmental Health Criteria 176. WHO. Geneva.
• Integrated Pollution Prevention an Control (IPPC), 2002, Reference Document on Best Available Techniques in the Large Volume Organic Chemical Industry, EC, Seville, Spain.

• IUCLID, 2000. IUCLID Datasheet 1,2-Dichloroethane. ISBN 92–828–8641–7. Ispra, Italy.

• Ministerio de Medio Ambiente, 2001. Spanish comments on the 2nd meeting of Experts Advisory Forum (EAF).
• RPA (Risk & Policy Analists), 2000, Socio-Economic Impacts of the Identification of Priority Hazardous Substances under the Water Framework Directive.

• Swedish EPA (Environmental Protection Agency) 2001, Information on emission sources for priority substances. Naturvårdsverket. Sweden.

• Statistisches Bundesamt, 1999,Statistiken zu Produktion und Außenhandel. Germany.

1

4K0976.01/O0004/JVS/TL

Fact sheets on production, use and release of priority substances in the WFDRoyal Haskoning

1,2-Dichloromethane, final draft

For official use only

aPPENDIX 1 lOCATION OF PRODUCTION

Coun-try / Town / Company / DCM / CHCl3 / TCE / CTC / 1,2-DE / C2Cl4 / 1,2,4-TCB / 1,2,3-TCB / HCB / SCCP / HCBD
B / Antwerpen / BASF Antwerpen N.V. / H
B / Tessenderlo / Limburgse Vinyl Maatschappij / H
B / Brussels / Solvay S.A. / H / H / H / H / H / H / L1)
D / Ludwigshafen / BASF AG / H / H
D / Leverkusen / Bayer AG / H / H / L1) / H
D / Frankfurt am Main / Celanese GmbH / H / H / H / H
D / Wolfen / Chemie GmbH Bitterfeld-Wolfen / H / H / L
D / Frankfurt am Main / Clariant GmbH / H
D / Stade / DOW Deutchland Inc. / H / H / H / H / H / L1)
D / Frankfurt/Main / EVC GmbH / H
D / Frankfurt/Main / Hoechst AG / H / H / H / H / H
D / Marl / Huels AG / H / H / H / H + L / L1)
D / Solingen / Solvay Alkali GmbH / H
D / Burgkirchen / Vinnolit Monomer GmbH / H
D / Burghausen / Wacker-Chemie GmbH / H / H / H
E / Barcelona / Erkimia, S.A. / H / H / H
E / Madrid / Aragones industrrias y energöa S.A. / H / H / H
E / Madrid / Viniclor S.A. / H
F / Paris la Defence / Atochem / H / H / H / H / H / ?1) / L1)
F / Paris / ESAR S.A. / L1)
F / Rueil Malmaison / Shell / H
GR / ? / ? / H
I / Ausimont Spa / Bollate / H / H / H
I / Milan / Caffaro S.p.A. / H
I / Torviscosa / Chimica del Friuli / H
I / Venezia / EVC S.p.A. / H
I / Milan / Enichem S.p.A. / H / H / H / H
I / Pieve Emanuele / S.A.I. Societa’ Approvv.
Indutriali Spa / H
NL / Amersfoort / Akzo Chemicals b.v. / H / H / H / H
NL / Rijswijk / Eurobrom B.V. / L
S / Steenungsund / Hydro Plast AB / H
UK / Runcorn, Cheshire / EVC Limited / H
UK / Runcorn, Cheshire / ICI Chemicals & Polymers Limited / H / ? 1) / H1) / H1) / H / ? 1) / ? 1)

1) Not reported is whether this implies production or importation

Information is derived from IUCLID 2000

H: High volume production

L: Low volume production

High production volume (HPV) chemical is defined as a chemical being produced or imported in quantitiy of at least 1000 tonnes per year in EU by at least one Industry.

A LPVC is a chemical which has been produced or imported in EU with a tonnage >10t/y but never more than 1000

4K0976.01/O0004/JVS/TL131-10-18

Fact sheets on production, use and release of priority substances in the WFDRoyal Haskoning

1,2-Dichloromethane, final draft

For official use only

Appendix 3: Release routes for 1,2-Dichloroethane

4K0976.01/O0004/JVS/TL131-10-18